Temperature-regulated nickel-catalyzed regiodivergent alkene hydroalkylation has been reported, yet there is a lack of a reasonable explanation for the regulation mechanism. Herein, we conduct a systematic analysis of the pertinent data, aiming to reveal the potential role and mechanism of temperature in regioselectivity. Alkyl radicals trapped by Ni(I) species are reasonably well-formed. Following this, entropic effects at different temperatures are found to be responsible for the regioselectivity turnover. Intramolecular transformation (β-H elimination) was less sensitive than the intermolecular step (radical addition and reductive elimination) for the entropy change; influencing the entropy response through temperature led to the regioselectivity regulation. These findings deepen our understanding of the influence of temperature on the regioselectivity of nickel-catalyzed alkene hydroalkylation.

中文翻译：

---

温度调节镍催化区域发散烯烃加氢烷基化中的熵效应


温度调节的镍催化区域发散烯烃加氢烷基化已有报道，但对其调节机制缺乏合理的解释。在此，我们对相关数据进行系统分析，旨在揭示温度在区域选择性中的潜在作用和机制。 Ni()物种捕获的烷基自由基结构相当良好。随后，发现不同温度下的熵效应是区域选择性转换的原因。分子内转化（β-H消除）对于熵变的敏感性不如分子间步骤（自由基加成和还原消除）；通过温度影响熵响应导致区域选择性调节。这些发现加深了我们对温度对镍催化烯烃加氢烷基化区域选择性影响的理解。